JP2006527274A - Fluorine resin silicone vulcanized rubber - Google Patents

Abstract

Fluoroplastics containing fluorocarbon resins and silicones are prepared by first mixing a fluorocarbon resin with a compatibilizer, then adding a curable organopolysiloxane with a radical initiator, and vulcanizing the organopolysiloxane in the mixture. The fluoroplastics can be processed by various techniques, such as extrusion, vacuum forming, injection molding, blow molding or compression molding, to fabricate plastic parts. The resulting fabricated parts can be re-processed (recycled) with little or no degradation of mechanical properties.

Description

  The present invention relates to a fluororesin containing a fluorocarbon resin and silicone. The fluororesin is made by first mixing the fluorocarbon resin with a compatibilizer, then adding a curable organopolysiloxane with a radical initiator, and vulcanizing the organopolysiloxane in the mixture. . The fluororesin of the present invention can be processed by various techniques such as extrusion, vacuum molding, injection molding, blow molding or compression molding to produce plastic parts. The resulting manufactured parts can be reworked (recycled) with little or no degradation of mechanical properties.

Dynamic vulcanization techniques are used in the manufacture of thermoplastic compositions based on fluorocarbon resins as taught, for example, in US Pat. No. 6,015,858. However, the composition of this' 858 patent is based on the use of a platinum catalyst to cure the silicone portion of the composition. The use of alternative curing systems, such as radical initiators, is not taught or suggested. In many applications, it is desirable to produce silicone based thermoplastic compositions by separate curing of fluorocarbon resins and silicone moieties. For example, platinum-free compositions may be desired in some applications, and in other cases where the economics of manufacturing are important, and may use less expensive curing agents such as radical initiators. Sometimes it is desired. Although inexpensive, radical initiators can cause other problems when used in the vulcanization process. In particular, their high volatility at high temperatures can cause safety problems.
U.S. Patent No. 6,015,858 "Vinylidene Fluoride-Based Thermoplastics (Overview and Commercial Aspects)", JSHumphrey, Jr. of Polymeric Material Encyclopedia, 1996 Version 1.1, CRC Press, NY "Tetrafluoroethylene Copolymers (Overview)", T. Takakura of Polymeric Material Encyclopedia, 1996 Version 1.1, CRC Press, NY "Fluorinated Plastics Amorphous" MH Hung, PR Resnick, BE Smart, WH Buck of Polymeric Material Encyclopedia, 1996 Version 1.1, CRC Press, NY "Fluoropolymers", KL. Ring, A. Leder, and M Ishikawa-Yamaki, Chemical Economics Handbook-SRI International 2000, Plastics and Resins 580.0700A U.S. Pat.No. 5,554,689 U.S. Patent No. 6,035,780 "Encyclopedia of Chemical Technology", Kirk-Othmer, 4th edition, Vol. 22, pp. 82-142, John Wiley & Sons, NY

  The present invention provides a method for producing a fluororesin composition comprising a fluorocarbon resin and silicone using vulcanization that cures silicone with a radical initiator.

The manufacturing method of the fluororesin composition is:
(I) Step of mixing the following components
(A) Fluorocarbon resin having a glass transition temperature higher than 23 ° C
(B) Compatibilizer
(C) any catalyst,
(II) mixing the product of step (I) with the following ingredients
(D) Silicone base containing curable organopolysiloxane
(E) a radical initiator in an amount sufficient to cure the organopolysiloxane, and
(III) vulcanizing the organopolysiloxane, wherein the weight ratio of the fluorocarbon resin (A) to the silicone base (D) in the elastomer base composition is in the range of 95: 5 to 30:70.

Furthermore, this invention relates to the fluororesin composition obtained by the method of this invention, and the processed article containing the thermoplastic composition.
The first step (I) of the method of the present invention is to mix the following components:
(A) Fluorocarbon resin having a glass transition temperature higher than 23 ° C
(B) Compatibilizer
(C) any catalyst

  The first step of the method produces a product referred to herein as "product of step (I)". Typically (although not required), the product of step (I) can be considered a modified fluorocarbon resin. The term “modified fluorocarbon resin” as used herein is chemically defined by the choice of components (A), (B), and optionally (C), and the attendant conditions used in this mixing step described below. Refers to a modified fluorocarbon resin that can be considered either modified or physically modified. Embodiments of the present invention for producing a chemically modified fluorocarbon resin are such that components (A), (B), and optionally (C) produce a reaction product of a fluorocarbon resin and a compatibilizer. Selected and mixed. Embodiments of the invention for producing a physically modified fluorocarbon resin include components (A), (B), and optionally (C) comprising a physical mixture product of a fluorocarbon resin and a compatibilizer. Selected to manufacture and mixed. In any case, if the product of step (I) produces a modified fluorocarbon resin, the fluorocarbon resin (A) produces a fluorocarbon / silicone mixture, which is further mixed with the silicone base composition, and the silicone As is vulcanized, it is modified to such a wind to produce a fluororesin composition having a continuous fluorocarbon resin phase and a discontinuous cured silicone phase (ie, an internal phase).

Component (A) of the present invention is a fluorocarbon (FC) resin. The FC resin can be any fluororesin having a melting point (T _m ) above room temperature (RT) or 23 ° C. and a glass transition temperature (T _g ) above room temperature or 23 ° C. “Glass transition temperature” means the temperature at which a polymer changes from a glassy state to a plastic state. The glass transition temperature can be measured by conventional methods such as dynamic mechanical analysis (DMA) and scanning differential calorimetry (DSC). Representative and non-limiting examples of FC resins include, for example, “Vinylidene Fluoride-Based Thermoplastics (Overview and Commercial Aspects)” in Polymer Material Encyclopedia, 1996 Version 1.1, CRC Press, NY, JSHumphrey, Jr., “Tetrafluoroethylene Copolymers ( Overview) ", T. Takakura," Fluorinated Plastics Amorphous ", MH Hung, PR Resnick, BE Smart, WH Buck and" Fluoropolymers ", KL. Ring, A. Leder, and M Ishikawa-Yamaki, Chemical Economics Handbook-SRI International One can find a general discussion of this type of material, such as 2000, Plastics and Resins 580.0700A, all of which are incorporated herein by reference. The FC resin is therefore considered to be a homopolymer, copolymer or terpolymer of said fluorine-containing monomer selected from the list: tetrafluoroethylene, vinylidene difluoride, chlorotrifluoroethylene, hexafluoropropylene, and vinyl fluoride. It is done. These monomers are not limited to the following, for example, vinyl compounds such as perfluoropropyl vinyl ether; olefin compounds such as ethylene or hexafluoropropylene; such as bromotrifluoroethylene and 1-bromo-2 It can also be copolymerized with copolymerizable monomers including halogen-containing polymerizable olefins such as 2-difluoroethylene. Commercially available examples include, but are not limited to, poly (vinylidene difluoride), (PVDF); poly (ethylene-tetrafluoroethylene), (E-TEF); hexafluoropropylene / vinylidene fluoride And (HFP-PVDF); tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride, (THV); and poly (ethylene-chlorotrifluoroethylene) (E-CTFE).

  It seems that the FC resin (A) may be a mixture of FC resins. However, in chemically modified embodiments, at least 2 wt%, alternatively at least 5 wt%, alternatively at least 10 wt% of the FC resin is at least one monomer capable of reacting with compatibilizer B, such as Olefin groups or the following groups: Polymers that must contain a monomer containing one of hydrogen bonded to carbon or chlorine bonded to carbon or bromine bonded to carbon or iodine bonded to carbon Or a copolymer.

  According to the method of the present invention, the FC resin (A) is mixed with the compatibilizer (B) in the presence of an optional catalyst to produce a modified FC resin. The structure of the compatibilizer is not critical. The function of the compatibilizing agent is a fluorine that has a continuous fluorocarbon resin phase and a discontinuous cured silicone phase (i.e., internal phase) when further mixed with the silicone base composition and vulcanized. Modifying the FC resin to produce the fluorocarbon / silicone mixture that the resin composition produces. Thus, the compatibilizer (B) promotes the mixing of the silicone base (D) and the FC resin (A) and has a continuous fluorocarbon resin phase and a discontinuous silicone phase (ie, an internal phase). It can be selected from hydrocarbons, organosiloxanes, fluorocarbons, or combinations thereof that are expected to modify the FC resin to produce a mixture. However, the compatibilizing agent or the resulting modified FC resin should not interfere with the curing of the organopolysiloxane component as will be described later.

  In the physically modified fluorocarbon embodiment, the compatibilizer (B) can be selected from any compatibilizer known in the art to enhance the mixing of the silicone base and the FC resin. Typically, such compatibilizers are reaction products of organopolysiloxanes and fluorocarbon polymers. Representative, non-limiting examples of such compatibilizers are described in US Pat. Nos. 5,554,689 and 6,035,780, both of which are hereby incorporated by reference.

  In chemically modified fluorocarbon embodiments, the compatibilizer (B) typically comprises (B ′) an organic (i.e., non-silicone) compound containing two or more olefinic groups, (B ″) Selected from the group of organopolysiloxanes containing at least two alkenyl groups and (B '' ') olefin functional silanes also containing at least one hydrolyzable group or one hydroxyl group bonded to the silicon atom can do.

  Organic compatibilizers (B ′) are, for example, diallyl phthalate, triallyl isocyanurate, 2,4,6-triallyloxy-1,3,5-triazine, triallyl trimesate, 1,5-hexadiene, 1, Mention may be made of compounds such as 7-octadiene, 2,2′-diallylbisphenol A, N, N′-diallyl tartaramide, diallyl urea, diallyl succinate and divinyl sulfone.

The compatibilizing agent (B ″) can be selected from linear, branched or cyclic organopolysiloxanes having at least two alkenyl groups in the molecule. Examples of such organopolysiloxanes are divinyltetramethyldisiloxane, cyclotrimethyltrivinyltrisiloxane, cyclo-tetramethyltetravinyltetrasiloxane, hydroxy-terminated block polymethylvinylsiloxane, hydroxy-terminated polymethylvinylsiloxane-co-poly. Includes dimethylsiloxane, dimethylvinylsiloxy-terminated polydimethylsiloxane, tetrakis (dimethylvinylsiloxy) silane and tris (dimethylvinylsiloxy) phenylsilane. Alternatively, the compatibilizer (B '') has a viscosity of 2-55,000 centistokes (mm ² / s) and contains vinyl terminated polymethylvinylsiloxane (Vi-[(MeViSiO) _x -(Me2SiO) _y ] -Vi). Alternatively, the compatibilizer (B '') is a hydroxy-terminated polymethylvinylsiloxane having a viscosity of about 35 m · Pa-s and containing 25-30% vinyl groups and 2-4% hydroxy groups attached to silicon [HO (MeViSiO) _x H] oligomer.

  The compatibilizing agent (B ′ ″) is typically at least one alkylene group containing vinylic unsaturation and at least one silicon-bonded moiety selected from hydrolyzable groups or hydroxyl groups. Silane containing Suitable hydrolyzable groups include alkoxy, aryloxy, acyloxy or amide groups. Examples of such silanes are vinyltriethoxysilane, vinyltrimethoxysilane, hexenyltriethoxysilane, hexenyltrimethoxysilane, methylvinyldisilanol, octenyltriethoxysilane, vinyltriacetoxysilane, vinyltris (2-ethoxyethoxy ) Silane, methylvinylbis (N-methylacetamido) silane, methylvinyldisianol.

  The curable organopolysiloxane portion of the silicone base component (D) described later can also serve as a compatibilizer. For example, using the catalyst (C), a portion of the silicone-based (D) curable organopolysiloxane can be first reacted with the FC resin to produce a modified FC resin. The modified FC resin is then mixed with the remaining silicone base (D) which further comprises a curable organopolysiloxane, and the organopolysiloxane is dynamically vulcanized as described below.

  The amount of compatibilizer used per 100 parts of FC resin can be determined by routine experimentation. Typically, 0.05 to 15 parts by weight or 0.1 to 5 parts of compatibilizer is used for each 100 parts of FC resin.

  Optional component (C) is a catalyst. Typically, the catalyst is used in chemically modified fluorocarbon embodiments. As such, it is typically a radical initiator selected from any organic compound known in the art for generating free radicals at elevated temperatures. The initiator is not particularly limited and may be any known azo or diazo compound, such as 2,2′-azobisisobutyronitrile, but is preferably hydroperoxide, diacyl peroxide. It is selected from organic peroxides such as oxides, ketone peroxides, peroxyesters, dialkyl peroxides, peroxydicarbonates, peroxyketals, peroxyacids, acylalkylsulfonyl peroxides and alkyl monoperoxydicarbonates. However, an important requirement is that the half-life of the initiator is sufficient to promote the reaction of the compatibilizer (B) with the FC resin (A) within the time and temperature limitations of the reaction step (I). It is very short. On the one hand, the modification temperature depends on the type of FC resin and the compatibilizer selected, but is typically low enough to practically match the uniform mixing of components (A) to (C). Specific examples of suitable peroxides that can be used by the method of the present invention include, among others, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, benzoyl peroxide, dicumyl peroxide, t-butyl peroxy O-toluate, cyclic peroxyketal, t-butyl hydroperoxide, t-butyl peroxypivalate, lauroyl peroxide and t-amyl peroxy 2-ethylhexanoate, di-t-butyl Peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, 2,2,4-trimethylpentyl-2-hydroperoxide, 2,5-bis (t-butylperoxy) -2,5- Dimethylhexyne-3, t-butyl-peroxy-3,5,5-trimethylhexanoate, cumene hydroperoxide, t-butylperoxybenzoate and diisopropylbenzene A hydroperoxide. An amount less than 2 parts by weight of peroxide per 100 parts of FC resin is typically used. Alternatively, 0.05-1 part, and 0.2-0.7 part can also be used.

  In addition to the specific limitations and process conditions associated with the catalyst selection described above, the reaction of step (I) can occur at a variety of conditions well known in the art that affect the reaction.

The second step (II) of the method of the invention comprises the product of step (I)
(D) a silicone base containing a curable organopolysiloxane,
(E) A step of mixing the organopolysiloxane with a sufficient amount of a radical initiator for curing.

Component (D) is a silicone base containing a curable organopolysiloxane (D ′) and optionally a filler (D ″). A curable organopolysiloxane is defined herein as any organopolysiloxane having at least two curable groups present in its molecule. Organopolysiloxanes are well known in the art and often contain any number of M units (R ₃ SiO _0.5 ), D units (R ₂ SiO), T units (RSiO _1.5 ) or Q units (SiO ₂ ) ( Wherein R is independently any monovalent hydrocarbon group). Alternatively, the organopolysiloxane has the following general formula: [R _m Si (O) _{4−m / 2} ] _n (wherein R is independently any monovalent hydrocarbon group, m = 1 to 3, where n is at least 2).

  The organopolysiloxane in the silicone base (D) must have at least two curable groups in its molecule. A curable group as used herein is defined as itself or another hydrocarbon group, or alternatively any hydrocarbon group that can react with a crosslinker to crosslink an organopolysiloxane. The This crosslinking produces a cured organopolysiloxane. A typical type of curable organopolysiloxane that can be used in the silicone base is an organopolysiloxane known in the art of producing silicone rubber upon curing. Representative and non-limiting examples of such organopolysiloxanes are “Encyclopedia of Chemical Technology”, Kirk-Othmer, 4th edition, Vol. 22, pages 82-142, John Wiley & Sons, NY (hereby incorporated by reference). Are incorporated into the document). Any organopolysiloxane can be selected as component (D) and if the combination with component (E) cures within the time and temperature limits of vulcanization step (III), component (E) As a free radical initiator would be selected. Depending on the choice of component (E) in such free radical-initiated crosslinking, any alkyl group such as, for example, methyl can be cured because they crosslink under conditions initiated by such free radicals. It can be considered as a basis.

  The amount of silicone phase defined herein as a combination of components (D) and (E) can vary depending on the amount of FC resin (A) used. However, it is possible to use FC resin (A) at a level of 30-95 wt%, alternatively 35-90 wt%, or alternatively 40-85 wt%, based on the total weight of components (A) to (E). Typical.

  It is also convenient to report the weight ratio of fluorocarbon resin (A) to silicone base (D), which is typically 95: 5 to 30:70, or 90:10 to 40:60, or 85: It is in the range of 15-40: 60.

  Typically, (D ′) is a diorganopolysiloxane rubber having at least 2 alkenyl groups having 2 to 20 carbon atoms, or diorganopolysiloxane and optionally (D ″) reinforcing filler It is. Specific examples of the alkenyl group include vinyl, allyl, butenyl, pentenyl, hexenyl and decenyl, preferably vinyl or hexenyl. The position of the alkenyl functional group is not critical and it can be attached at the end of the molecular chain, at a non-terminal position on the molecular chain, or at both positions. Typically, the alkenyl group is vinyl or hexenyl, and this group is present in the diorganopolysiloxane at a level of 0.0001-3 mol%, alternatively 0.0005-1 mol%. The remaining (ie, non-alkenyl) silicon-bonded diorganopolysiloxane organic groups are independently selected from hydrocarbon or halogenated hydrocarbon groups free of aliphatic unsaturation. Specific examples thereof include alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; cycloalkyl groups such as cyclohexyl and cycloheptyl; Aryl groups having 6 to 12 carbon atoms such as phenyl, tolyl and xylyl; aralkyl groups having 7 to 20 carbon atoms such as benzyl and phenylethyl; and 3,3,3-trifluoropropyl And halogenated alkyl groups having 1 to 20 carbon atoms, such as chloromethyl. Of course, it should be understood that these groups are selected such that the diorganopolysiloxane has a glass transition temperature (or melting point) below room temperature, and thus the cured polymer is an elastomer. Typically, the organic groups in the diorganopolysiloxane bonded to non-alkenyl silicon constitute at least 85 mol% of the organic groups in the diorganopolysiloxane, or alternatively at least 90 mol%.

  Thus, the polydiorganopolysiloxane (D) can be a homopolymer, copolymer or terpolymer containing such organic groups. Examples are inter alia copolymers containing dimethylsiloxy units and phenylmethylsiloxy units, copolymers containing dimethylsiloxy units and 3,3,3-trifluoropropylmethylsiloxy units, copolymers containing dimethylsiloxy units and diphenylsiloxy units and dimethylsiloxy. An interpolymer comprising units, diphenylsiloxy units and phenylmethylsiloxy units. Also, the molecular structure is not critical and examples include linear and partially branched linear structures, with linear systems being most typical.

  Specific examples of diorganopolysiloxane (D) are trimethylsiloxy endblocked dimethylsiloxane-methylvinylsiloxane copolymer; trimethylsiloxy endblocked methylphenylsiloxane-dimethylsiloxane-methylvinylsiloxane copolymer; trimethylsiloxy endblocked 3,3, 3-trifluoropropylmethylsiloxane copolymer; trimethylsiloxy endblock 3,3,3-trifluoropropylmethyl-methylvinylsiloxane copolymer; dimethylvinylsiloxy endblock dimethylpolysiloxane; dimethylvinylsiloxy endblock dimethylsiloxane-methylvinylsiloxane copolymer Dimethylvinylsiloxy-terminated methylphenylpolysiloxane; dimethylvinylsiloxy-terminated block methylphenylsiloxane-di Chill siloxane - methyl vinyl siloxane copolymer; and at least one terminal group contains a similar copolymer is dimethylhydroxysiloxy. Typical systems for low temperature applications are methylphenylsiloxane-dimethylsiloxane-methylvinylsiloxane copolymer and diphenylsiloxane-dimethylsiloxane-methylvinylsiloxane copolymer, especially those having a molar content of dimethylsiloxane units of about 85-95. Includes what is%.

  Component (D) is a combination of two or more organopolysiloxanes. Alternatively, the diorganopolysiloxane (D) is a linear polydimethylsiloxane homopolymer, preferably terminated with a vinyl group at each end of the molecule, or it has at least one vinyl group in its backbone. And such homopolymers.

  Typically, the molecular weight of the diorganopolysiloxane is sufficient to give a Williams plasticity number of at least about 30 as measured by American Society for Testing and Materials (ASTM) test method D926. There is no absolute upper limit on the plasticity of component (D ′), but this value is generally limited when considering the processability in conventional mixing equipment. Typically, the plasticity should be 40-200, or 50-150.

  Methods for producing diorganopolysiloxanes containing highly viscous unsaturated groups are well known and need not be discussed in detail in this specification. For example, a typical process for preparing alkenyl functional polymers involves the base catalyzed equilibration of cyclic and / or linear diorganopolysiloxanes in the presence of similar alkenyl functional ones.

Optional component (D '') is any filler known to reinforce diorganopolysiloxane (D '), preferably fumed with a specific surface area of, for example, at least about 50 m ² / gram. Selected from finely divided thermally stable minerals such as silica, precipitated silica, silica airgel and titanium dioxide. Fumed silica is a typical reinforcing filler based on its high surface area, which can be up to 450 m ² / gram. Alternatively, fumed silica having a surface area of 50 to 400 m ² / gram, or alternatively 90 to 380 m ² / gram, can be used. The filler is added at a level of about 5-150 parts by weight per 100 parts by weight of diorganopolysiloxane (D ′), alternatively 10-100, or alternatively 15-70 parts by weight.

  Fillers are typically treated to make their surfaces oleophilic as is typically practiced in silicone rubber technology. This is achieved by reacting silica with a liquid organosilicone compound containing a silanol group or a hydrolyzable precursor of a silanol group. A compound that can be used as an agent to treat fillers, also called anti-creping agents or plasticizers in silicone rubber technology, is a low molecular weight liquid hydroxy- or alkoxy-terminated polydiorganosiloxane, hexa Ingredients such as organodisiloxane, cyclodimethylsilazane and hexaorganodisilazane are included. Component (D) can optionally include other materials commonly used in silicone rubber formulations, including but not limited to antioxidants, cross-linking additives, treating agents, pigments or the art. Other additives, which are not negatively affected by the silicone curing step (III).

  Component (E) is selected to provide free radical curing of the organopolysiloxane. The radical initiator (E) can be selected from any of the free radical initiators previously described for selecting component (B).

  In addition to the main components (A) to (E), one or more optional additives (F) can be incorporated into the fluororesin composition of the present invention. These optional additives include the following non-limiting examples: bulking fillers such as quartz, calcium carbonate and diatomaceous earth; pigments such as iron oxide and titanium oxide; such as carbon black and finely divided metal Fillers; heat stabilizers such as hydrated cerium oxide, calcium hydroxide, magnesium oxide; such as halogenated hydrocarbons, alumina trihydrate, magnesium hydroxide, wollastonite, organophosphorus compounds Flame retardants and other flame retardants; and other additives known in the art. These additives are typically added to the final vulcanized composition, but may be added at any point in the manufacturing provided they do not interfere with the vulcanization mechanism. These additives may be the same as or different from the additional components added to produce the cured elastomer composition described below.

  The third step (III) of the method of the present invention is vulcanization of the organopolysiloxane. Vulcanization can occur statically or dynamically. Dynamic vulcanization used in the present invention refers to a vulcanization process that occurs with continuous mixing of the fluororesin composition. The continuous mixing is the same as the mixing that performs step (II), i.e., the mixing of step (II), or alternatively the mixing can occur following step (II). possible. Alternatively, the vulcanization can occur statically. Static vulcanization refers to vulcanizing the organopolysiloxane without further mixing the product of step (II). For example, the product of the mixture of step (II) can simply be subjected to an organopolysiloxane curing process such as heating of the product of step (II).

  Thereby, the fluororesin composition is typically obtained by completely dispersing the silicone base (D) in the modified FC resin and then vulcanizing the silicone base using a radical initiator, component (E). To be manufactured. Mixing can be carried out in any apparatus capable of uniformly dispersing the components in the FC resin, such as a closed mixer and an extruder. Alternatively, the mixing steps (I) and (II) of the method and the dynamic vulcanization embodiment of step (III) can be accomplished by using a twin screw extruder. As noted previously, the FC resin must be modified before adding components (D) to (F). After modification of the FC resin, the order of mixing components (D) to (F) can be determined by those skilled in the art. Typically (F) will be added after (E), but it is not critical as long as (F) does not interfere with the curing of the elastomeric phase (e.g. (F) is an FC resin or Can be pre-mixed with the base).

  In a typical mixing procedure, FC resin (A) and compatibilizer (B) are first mixed in a mixer at a controlled temperature and then catalyst (C) is added when used. . The temperature used during this (chemical) denaturation step is determined experimentally to give the optimum half-life of the initiator (C). During this step, component (C) is in the FC resin / compatibilizer combination, while it decomposes simultaneously to the extent sufficient to graft the compatibilizer to FC resin (A) within the allotted time. Must be thoroughly mixed. If the temperature is too high, the initiator will decompose prematurely and the modification of the FC resin will be insufficient, and if the temperature is too low, the initiator will not be sufficiently decomposed and only a slightly modified FC resin will be produced. It is preferred to thoroughly mix the compatibilizer with the FC resin before adding the catalyst (C).

  Modification of the FC resin can be accomplished in one step just before adding the silicone base (D) and the radical initiator (E). Alternatively, the FC resin is modified from the mixer in the next step, first modifying the FC resin and then adding the modified FC resin back to the mixer along with the silicone base (D) and the radical initiator (E). It can be manufactured in two steps, a step to remove it.

  Any mixing technique known for mixing such fluoropolymer materials can be used in the method of the present invention, but typically uses an extrusion process. Mixing steps (I) and (II) and step (III) when dynamic vulcanization is used can be carried out using a twin screw extruder. In one embodiment of the method of the present invention, the mixing takes place in a twin screw extruder in less than 5 minutes.

  Additional components can be added to the fluororesin silicone composition. These include the step of mixing other fluororesin or other fluororesin silicone composition into the fluororesin silicone composition of the present invention. These additional components can also be any components or materials typically added to fluororesins. Typically, these components can be selected from fillers and processing aids. Many commercially available fluoropolymers may already contain these components.

  The fluororesin of the present invention can be processed by conventional techniques such as extrusion, vacuum molding, injection molding, blow molding or compression molding to produce resin parts. Furthermore, these compositions can be reworked (recycled) with little or no degradation of mechanical properties. These novel fluororesins have utility in wire or cable insulation, such as plenum wires, automobile and appliance parts, belts, hoses, structural seal manufacturing and general rubber applications.

(Example)
The following examples are provided to further illustrate the compositions and methods of the present invention and are not to be construed as limiting the invention, which is outlined in the appended claims. Is drawn. All parts and percentages in the examples are on a weight basis and all measurements were obtained at about 23 ° C. unless otherwise indicated.
The raw material, GP-30, is a silicone rubber base marketed by Dow Corning Corporation as Silastic® GP-30 Silicone Rubber.
GP-50 is a silicone rubber base marketed by Dow Corning Corporation as Silastic® GP-50 Silicone Rubber.
LCS-755 is a silicone rubber base marketed by Dow Corning Corporation as Silastic® LCS-755 Silicone Rubber.
LS-2840 is a fluorosilicone rubber base marketed by Dow Corning Corporation as Silastic® LS-2840 Fluorosilicone Rubber, Gama-Sperse® CS-11 marketed by Georgia Marble Company 5 parts are included.
Compatibilizer 1 is a hydroxy end-blocked methylvinylsiloxane oligomer having a viscosity of about 35 mPa-s and containing 30% —CH═CH ₂ groups and 3% OH groups.
Compatibilizer 2 is a fluorocarbon terpolymer having a Mooney viscosity (ML1 + 10) 21 and having one end terminated with iodine.
TAIC is triallyl isocyanurate (CAS # 1025-15-6) (72%) adsorbed on calcium silicate and is marketed by Akrochem Corporation as AkrosorbTM 19251 (B) TAIC (72) Yes.
THV220G is a fluororesin terpolymer composed of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride and having a melting point of 120 ° C., and is marketed as Dyneon ™ Fluorothermoplastics THV 220G by Dyneon A 3M Company.
THV610G is a fluororesin terpolymer composed of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride and having a melting point of 185 ° C., and is marketed by Dyneon A 3M Company as Dyneon ™ Fluorothermoplastics THV 610G.
Kynar 2500 is a fluoropolymer copolymer and is marketed as Kynar Flex® 2500 by ATOFINA Chemicals, Inc.
Kynar 2750 is a fluoropolymer copolymer and is marketed as Kynar Flex® 2750 by ATOFINA Chemicals, Inc.
Kynar 460 is a fluoropolymer homopolymer and is marketed by ATOFINA Chemicals, Inc. as Kynar Flex® 460.
Trigonox 101- is 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane (CAS # 78-63-7), which is a TRIGONOX® 101 by Akzo Novel Chemicals, Inc. Is commercially available.
Trigonox 145- is 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3 (CAS # 1068-27-5) supported by 45% on calcium carbonate, Akzo Novel It is marketed by Chemicals, Inc. as TRIGONOX® 145-45B-pd.
Trigonox A-W70- is a 70% aqueous solution of tert-butyl hydroperoxide (CAS # 75-91-2) and is marketed by Akzo Novel Chemicals, Inc. as TRIGONOX (registered trademark) A-W70.

(Example 1)
THV220G (235.79 g) was added to a 310 ml Haake bowl equipped with a rotating rotor at 170 ° C. and 50 rpm. Five minutes after melting, Compatibilizer 1 (2.2 g) was added. The rotor speed was reduced to 10 rpm and all compatibilizer 1 was added. The rotor speed was then increased stepwise to 60 rpm over 20 minutes and mixed for 5 minutes. Trigonox 101 (0.6 g) was then added. After 5 minutes, GP-50 (91.86 g) was added and mixed for 5 minutes. Trigonox 101 (1.60 g) was added and the resulting resin composition was mixed for about 5 minutes until the torque was stable.

  The resin composition was hot pressed into a plaque. A physical property test was conducted 24 hours after the compression molding. Tensile and elongation were measured at D 500 mm / min according to ASTM D412 Die Standard. Example 1 gave a tensile strength of 8.5 MPa and an elongation of 410%.

(Example 2)
Kynar 2500 (215.3 g) was added to a 310 ml Haake bowl equipped with a rotating rotor at 165 ° C. and 60 rpm. Five minutes after melting, compatibilizer 1 (5.3 g) was added. The rotor speed was reduced to 5 rpm and all compatibilizer 1 was added. The rotor speed was then increased stepwise to 60 rpm over 15 minutes and mixed for 10 minutes. Trigonox 101 (1.29 g) was then added. After 10 minutes, GP-50 (92.0 g) was added and mixed for 5 minutes. Trigonox 101 (2.8 g) was added and the resulting resin composition was mixed for about 5 minutes until the torque was stable.

  The resin composition was hot pressed into plaques. A physical property test was conducted 24 hours after the compression molding. Tensile and elongation were measured at D 500 mm / min according to ASTM D412 Die Standard. Example 2 had a tensile strength of 8.5 MPa and an elongation of 302%.

(Example 3)
THV220G (235.8 g) was added to a 310 ml Haake bowl equipped with a rotating rotor at 185 ° C. and 60 rpm. Compatibilizer 1 (2.3 g) was added 5 minutes after it melted. The rotor speed was reduced to 5 rpm and all compatibilizer 1 was added. The rotor speed was then increased stepwise to 60 rpm over 10 minutes and mixed for 5 minutes. Trigonox 101 (0.6 g) was then added. After 10 minutes, GP-30 (92.66 g) was added and mixed for 5 minutes. Trigonox 101 (1.38 g) was added and the resulting resin composition was mixed for about 5 minutes until the torque was stable.
The resin composition was hot pressed into plaques. A physical property test was conducted 24 hours after the compression molding. Tensile and elongation were measured at D 500 mm / min according to ASTM D412 Die Standard. Example 3 had a tensile strength of 10.7 MPa and an elongation of 445%.

(Example 4)
Kynar 460 (210 g) was added to a Haake Rheomix 3000 bowl equipped with a Banbury rotor at 165 ° C. and 50 rpm and mixed until it melted. TAIC (3g) and Trigonox 145 (1g) were added. The rotor speed was increased to 75 rpm and mixed for 10 minutes. GP-50 (140 g) was added and mixed for 10 minutes. Trigonox A-W70 (2 g) was added and the resulting resin composition was mixed for about 5 minutes. Sample 4A was removed from Haaka and statically cured in a press at 225 ° C. for 10 minutes. Sample 4B was dynamically cured at 150 rpm in Haake and mixed until the torque was stable. The resin composition was hot pressed into plaques. Tensile and elongation were measured at D 500 mm / min according to ASTM D412 Die Standard. Example 4A had a tensile strength of 8.3 MPa and an elongation of 12% and a 39 Shore D Durometer. Example 4B had a tensile strength of 7.2 MPa and an elongation of 14% and a 33 Shore D durometer.

(Example 5)
For Kynar 2750 (223 g), LS-2840 (180 g) and Sample 5B and Sample 5C only Compatibilizer 2 (3 g) is added to the Haake Rheomix 3000 ball with a 50 rpm Banbury rotor and the chamber temperature until the fluoropolymer melts Mixed at 200 ° C. Trigonox A-W70 (2.5 g) was added and the resulting resin composition was mixed at about 100 rpm. Samples 5A and 5B were mixed until the decomposition temperature of the peroxide was reached to dynamically cure the silicone. Sample 5C was removed from Haaka after 10 minutes of mixing and statically cured in a press at 225 ° C. for 10 minutes. The resin composition was hot pressed into plaques. Tensile and elongation were measured at D 500 mm / min according to ASTM D412 Die Standard. Example 5A had a tensile strength of 6.4 MPa and an elongation of 206% and a 29 Shore D durometer. Example 5B had a tensile strength of 8.0 MPa and an elongation of 294% and a 30 Shore D durometer. Example 5C had a tensile strength of 6.0 MPa and an elongation of 210% and a 20 Shore D durometer.

(Example 6)
For THV610G (300 g) and Samples 6B and 6C only Compatibilizer 1 (3 g) was added to a Haake Rheomix 3000 ball equipped with a 25 rpm Banbury rotor and mixed at a chamber temperature of about 200 ° C. until the fluoropolymer melted. For sample 6B and sample 6C only, Trigonox 145 (1 g) was added. The rotor speed was increased to 125 rpm and mixed for 10 minutes. LCS-755 (115 g) was added and mixed for 2 minutes. Trigonox A-W70 (2.0 g) was added. Samples 6A and 6B were mixed until the decomposition temperature of the peroxide was reached to dynamically cure the silicone. Sample 6C was removed from Haaka after 10 minutes of mixing and statically cured in a press at 225 ° C. for 10 minutes. The resin composition was hot pressed into plaques. Tensile and elongation were measured at D 500 mm / min according to ASTM D412 Die Standard. Example 6A had a tensile strength of 4.2 MPa and an elongation of 206% and a 28 Shore D durometer. Example 6B had a tensile strength of 7.4 MPa and an elongation of 305% and a 31 Shore D durometer. Example 6C had a tensile strength of 5.6 MPa and an elongation of 99% and a 31 Shore D durometer.

Claims (13)

(I) Step of mixing the following components
(A) Fluorocarbon resin having a glass transition temperature higher than 23 ° C
(B) Compatibilizer
(C) any catalyst,
(II) mixing the product of step (I) with the following ingredients
(D) Silicone base containing curable organopolysiloxane
(E) a radical initiator in an amount sufficient to cure the organopolysiloxane and
(III) a fluororesin comprising a step of vulcanizing an organopolysiloxane, wherein the weight ratio of the fluorocarbon resin (A) to the silicone base (D) in the elastomer base composition is in the range of 95: 5 to 30:70 A method for producing the composition.   The fluorocarbon resin (A) is a fluoropolymer homopolymer, copolymer or terpolymer comprising a monomer selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, and vinylidene fluoride monomers. Item 2. The method according to Item 1.   Compatibilizer (B) binds to (B ′) an organic compound containing two or more olefin groups, (B ″) an organopolysiloxane containing at least two alkenyl groups and (B ′ ″) a silicon atom 2. The method of claim 1 selected from the group of olefin functional silanes that also contain at least one hydrolyzable group or at least one hydroxyl group.   The method according to claim 1, wherein the compatibilizing agent (B) is a hydroxy-end-blocked methylvinylsiloxane.   The process according to claim 1, wherein an optional catalyst (C) is present and is an organic peroxide.   The curable organopolysiloxane contains at least 2 alkenyl groups having 2 to 20 carbon atoms and is sufficient to give a William plasticity of at least 30 as measured by American Society for Testing and Materials (ASTM) test method D926 2. The method according to claim 1, which is a diorganopolysiloxane rubber having an appropriate molecular weight.   2. The method according to claim 1, wherein the radical initiator is an organic peroxide.   2. The method according to claim 1, wherein the vulcanization step (III) is dynamic vulcanization.   The method of claim 8, wherein the dynamic vulcanization occurs by an extrusion process.   The method of claim 9 wherein the extrusion process occurs in a twin screw extruder.   The method according to claim 1, wherein the vulcanization step (III) is static vulcanization.   A fluororesin composition produced by the method according to any one of claims 1 to 11. 13. A processed article comprising the fluororesin composition according to claim 12.